High oxirane fatty esters



United States Patent 3,377,304 HIGH OXIRANE FATTY ESTERS Frank E.Kuester, La Grange, Ill., and Philip H. Rhodes,

Cincinnati, Ohio, assignors to Swift & Company, Chicago, 1ll., acorporation of Illinois No Drawing. Continuation-impart of applicationSer. No. 807,985, Apr. 22, 1959. This application May 18, 1964, Ser. No.368,389

6 Claims. (Cl. 260-23) This application is a continuation-in-part of ourcopending application Ser. No. 807,985, filed Apr. 22, 1959, nowabandoned.

This invention relates to polyvinyl resin compositions having improvedproperties and more particularly to polyvinyl resins plasticized withhigh oxirane epoxy fatty acid esters.

Polyvinyl resins, particularly polyvinyl halide resins, are employed ina wide range of applications and in many of these applications it isnecessary to plasticize the resin. The physical properties of the resindepend to a great degree upon the amount and type of plasticizerincorporated therein. Usually, while the flexibility, tear resistance,"and elongation of vinyls increase with increased plasticizer content,the tensile strength and hardness decrease. Many plasticizers have beenemployed in the formulation of vinyl resins, and While some of theseplasticizers offer advantages in some respects, they possessshortcomings in other respects, and this results in the necessity forcombinations of two or more plasticizers, each having certain desirableproperties that are lacking in some others.

It is, therefore, an object of the present invention to provide a vinylplasticizer composition which imparts to the resin more of theadvantages desired in a plasticized resin while exhibiting less of theundesirable characteristics usually associated with prior artplasticizers.

It is a further object of this invention to provide novelplasticizer-stabilizer compositions which, when combined with vinylresins, impart improved physical properties to the resin and whichpossess an unusually high degree of compatibility with the resin.

Another object of the invention is the provision of a plasticized vinylhalide resin composition having a high resistance to heat and lightdegradation.

Still another object is to provide fiexible vinyl halide film ofimproved stability which is nontoxic and therefore adaptable for use inthe packaging of foods.

Additional objects and advantages if not specifically set out willbecome apparent during the course of the disclosure which follows:

The plasticizer compositions of the present invention comprise esters ofhigh oxirane containing higher fatty acids with mono, di, and polyhydricaliphatic alcohols. These esters are low viscosity oils possessinglittle or no color. The esters may be characterized as high oxiranefatty materials containing a plurality of oxirane rings or epoxy groupsat those points in the fatty acyl radical which are normally occupied bydouble bonds in the original nonepoxidized fatty acid or ester.

Monohydric and dihydric alcohol esters of the high oxirane fatty esterswhich are contemplated include the aliphatic alkyl esters wherein thealcohol portion of the ester is a monohydric alcohol having 1-8 carbons,and aliphatic alcohol esters of dihydric alcohols having 2-6 carbonatoms. Lower aliphatic alcohols of the olefin and paraflin series andwhich may be substituted if desired with noninterfering substituents aresuitable. The epoxy fatty acid component is made up of epoxy fatty acidsof 10-30 carbons having an oxirane content above about 8.8. Suitablemonohydric alcohols providing the alcohol moiety of the ester includemethyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl,heptyl, and octyl alcohols.

Benzenoid alcohols which may be employed in preparing the ester arethose benzoid alcohols having less than 10 carbons and include benzyl,p'henyl, 2-phenylethyl, 1- phenylethyl and nuclear methylated phenylalcohols. Dihydric. alcohols include the lower glycols, such as ethyleneglycol, 1,2 propane diol, 1,3 propane diol, dimethyl ethylene glycol,trimethylene glycol, tetramethylene gly col, and up to hexamethyleneglycol. Generally the lower monohydric alcohol esters provide a lessviscous dispersion of the vinyl when the resin and plasticizer are mixedthan the higher mono-hydric alcohol esters. The lower alcohol esters arealso more volatile than the higher alcohol esters, and therefore for agiven preparation a balance between viscosity requirements andvolatility requirements is possible by careful selection of the ester.The dihydric and polyhydric alcohol esters act similarly.

Methods for determining the oxirane content of a given high-oxiraneester or mixture of esters are well-known and, while the preferredtechnique is American Oil chemists Society tentative method Cd-9-57,described in Ofiicial and Tentative Methods of the American Oil Ohemists Society, Second Edition, 1946, including Additions and Revisions1947 to 1958, inclusive, other analytical methods known in the art maybe employed. The method described by A. J. Durbetaki, AnalyticalChemistry, volume 28, No. 12, December 1956, pp. 2000-2001, is alsosuitable for determining oxirane content.

The polyhydric alcohol esters of the high oxirane fatty acids includethe tri-., tetra-, penta-, and hexahydric alcohol esters of the fattyacid moiety. Included within this group are those aliphatic alcoholshaving 3-6 carbons and 3 or more alcohol groups. These alcohols includeglycerol, erythritol, pentaerythritol, and hexitols such as mannitol andsorbitol.

The epoxy fatty acid portion of the novel plasticizer is made up ofthose fatty acids and mixtures of fatty acids having 10-30 carbons andan oxirane content above about 8.8. The saturated acid content of thefatty acid mixture should preferably not exceed about 10-15%. Thereforethe presence of such saturated acids as stearic acid, palmitic acid,myristic acid, etc., should for best results be held to a minimum.Moreover, the fatty acids should not be hydroxylated or containconjugated unsaturation. Mixtures containing epoxystear-ic,diepoxystearic, triepoxystearic, diepoxyeicosanoic, triep oxyeicosanoic,diepoxydocosanoic, triepoxydocosanoic, tetraepoxydocosanoic andpentaepoxytetracosanoic acids are a very desirable source of the oxiranesupplying radical.

Suitable naturally occurring oils which, when substantially completelyepoxidized, may be used in practicing the invention are those vegetableand marine triglycerides containing not more than about 10-15% saturatedfatty acids and containing unsaturated fatty acids predominantly. Thesenaturally occurring oils should have a degree of unsaturationrepresented by an iodine value .of about to about 205 and the fattyacids are neither hydroxylated nor possess conjugated unsaturation. Thelinolenic acid oils which are primarily triglycerides of linoleic, andlinolenic acids are preferred. Among those oils which may be employedare highly epoxidized perilla oil and highly epoxidized linseed oil.These naturally occurring highly unsaturated oils also provide avaluable source of fatty acid mixtures. Purified and concentrated fattyacid mixtures containing a large amount of unsaturated fatty acids maybe obtained from such vegetable oils as soybean oil and tall .oil orfrom the fish oils. These materials must first be refined to concentratethe more highly unsaturated components and remove .at least a portion ofthe saturated acids. The fish oils in particular have a high degree ofunsaturation as represented by iodine values as high as 270 but containtoo great a quantity of saturated acids.

3 Therefore these materials are first treated to reduce the saturatedacid content below about -15% In order for the epoxy fatty acid ester tobe effective in providing in the esters the desired compatibility, it isnecessary that the fatty acid or mixture of fatty acids forming thefatty acyl portion of the ester have an oxirane content above about 8.8and, as a practical matter, in the range 8.8-12.3. The preferred oxiranecontent of the fatty acyl component is around 9.0-9.5. This preferredoxirane content is easily obtained from a mixture of epoxy containingfatty acids containing less than about satur ated fatty acids andconsisting predominantly of the di-, tri-, and tetra-ethanoic acids. Aparticularly desirable fatty acid mixture is one containing less thanabout 35% epoxy linoleic acid and the total epoxy linoleic-epoxylinolenic acid content being above about 60%. This preferred mixture isreadily obtained from naturaly occurring lin seed oil or perilla oil bysubjecting such oils, provided they possess an iodine value above about170, to an epoxidation treatment such as is described hereinafter.

Substantially completely epoxidized triglycerides having anoxirane-oxygen content of about 8.89.2% and an iodine value of 0-12provide, in combination with nonreactive polyvinyl chloride resins, amost unique product. Substantially completely epoxidized linseed oil isparticularly preferred since this composition can be prepared fromreadily available naturally-occurring triglyceride oil to possess a highoxirane value, low residual unsaturation and low byproducts such aspolymeric materials and hydroxylated substituents. Epoxized linseed oilhaving the specified oxirane-oxygen value and iodine value and lowhydroxyl substitution represented by an infrared absorptivity at 2.9microns of 0.020 maximum (007-020) is most effective. Absorptivity at2.9 microns is run in carbon disulfide solution with a Perkin-ElmerModel 21 Spectrophotometer using a base line drawn from minima at eitherside of the peak at 2.9 microns.

This composition has a high chemical purity and its low viscosity(Gardner-Holdt) of V-maximum of 8.8 poises maximum is evidence of lowpolymer content. The composition has an acid number of 0.3 maximum, andis light in color, having a Gardner color of less than 1, and thus doesnot introduce any significant amount of color into clear plastics inwhich it is formulated.

Although the aforementioned compositions exert their greatest effect andprovide the greatest benefit with vinyl type resins, other thermoplasticand thermosetting resins, such as the cellulose esters and natural andsynthetic rubber, may advantageously be compounded with the plasticizersof this invention. Accordingly, the invention is primarily applicable topolyvinyl resins in general and particularly to polyvinyl chloride,polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, and vinylchloridevinylidene chloride copolymers. Those thermoplastic vinyl halidecopolymers containing greater than 50% of the monomer units as vinylhalide units are preferred. The Vinylite resins, such as Vinylite VAGH,Vinylite VYHH, Vinylite VMCH, and the Geon resins, such as Geon 103 andGeon 121, are specific examples of suitable vinyl halide polymers.Vinylite VAGH is reported to contain 91% vinyl chloride units, 3% vinylacetate units, and 6% vinyl alcohol. Vinylite VYHH contains 87% vinylchloride and 13% vinyl acetate. Vinylite VMCH contains about 86% vinylchloride, 13% vinyl acetate, and 1% maleic acid. Geon 121 and Geon 103contain in excess of 90% vinyl chloride units and generally 96100% vinylchloride uni-ts.

Vinyl halide resins with which the compositions of the invention aremost eifective are those polyvinyl chloride and polyvinylidene chloridehomopolymers and copolymers which are plasticized or flexibilized withthe high oxirane esters but do not react with the esters. Thus thosepolymers and copolymers of vinyl and vinylidene halide which are free ofpoly unsaturated ethers and esters are contemplated. The resins of theinvention are free of multiethylenically unsaturated monomers such asdiallyl succinate, diallyl maleate, divinyl ether and such monomerswhich could react with the epoxidized ester and promote objectionablestiifening and loss of flexibility of the plasticized vinyl polymer.

While the high oxirane content of the epoxy containing material appearsto provide a most important advantage in the processing benefits andphysical characteristics of products made from the mixture of epoxideand vinyl, the high oxirane content of the epoxy composition combinedwith a vinyl stabilizer appears to impart extremely high stability tothe resin composition. For example, in the production of polyvinylchloride films from a polyvinyl chloride composition containing a highoxirane fatty ester and a stabilizer comprising an alkaline earth metalsalt of a higher aliphatic organic acid, it is possible to operate anextruder for a long period of time without shutdown and with a minimumamount of burning and charting of the resin composition in the extruder.With conventional vinyls and vinyls plasticized with well-knownplasticizers such as dioctyl phthalate and epoxy plasticizers of lessthan the minimum oxirane content, it is necessary to frequently shutdown extruders being employed to form the vinyl because of anaccumulation of charred resin in the extruder resulting from heatdegradation. Specific stabilizers which may advantageously be employedinclude zinc octoate, barium octoate, calcium octoate, and mixtures ofbarium-cadmium salts of fatty acids as barium-cadmium laurate orbarium-cadmium stearate. Still other stabilizers are the typical vinylstabilizers such as dibutyl tin dilaurate, zinc dilaurate, the leadcarbonates and stearates, barium-cadmium phosphites, etc. A particularlyvaluable stabilizer mixture employed in the compositions of the presentinvention is a mixture of zinc and calcium stearates. This compositionis unusually valuable because it appears to inhibit heat degradationwhile imparting improved lubricating qualities to the polyvinyl chlorideresin. Moreover, it is sufficiently non-toxic that the film can be usedin wrapping foods.

Fillers, pigments, lubricants, antistatic agents, and antiblockingagents may also be employed in the composition where desirable. Aparticularly effective static reducer is the product resulting from thecondensation of 1 mol of tetraethylene pentamine with 5 mols of stearicacid.

The following examples which are intended to be illustrative only andshould in no Way be considered limitative are included herein tofacilitate an understanding of the invention.

EPOXIDATION OF UNSATURATED FATTY ACID OR MIXTURES THEREOF Inasmuch asheavy metals deleteriously aifect the epoxidation reaction, it isadvisable to conduct the epoxidation in glass equipment or in carefullyprepared metal reaction vessels. The metal equipment should beconditioned by nitric acid passivation before the first use to removewelding beads, metal filings, and other sources of heavy metalcontamination. Also the reactants should be free of heavy metals. Theprocedures which are described hereafter were conducted in 316 stainlesssteel equipment.

Example I A benzene solution comprising 780 lbs. benzene and 850 lbs.linseed oil is charged to the reaction vessel and the solution isvigorously agitated as 525 lbs. of 50% hydrogen peroxide is added. Thesulfuric acid catalyst (5.3 lbs.) is diluted with 5 lbs. of peroxide,and this mixture is then added to the reaction vessel. The wellagitatedmixture is then heated to F. and 90% formic acid is slowly added to theheated mixture. The reaction is exothermic and the temperature ispermitted to rise to about -162 F., at which time cooling is employed tomaintain this approximate temperature. The

addition of 45 lbs. of formic acid requires about 2 hours. acidcomponents from naturally occurring fatty acid The total reaction timeincluding this 2-hour addition esters and fatty alcohols and mixturesthereof follows: period is about 9 hours, and the reaction temperatureranges between 160-l68 F. After cooling, the aqueous Example In layer ofthe product is drawn off and the remaining 5 Linseed oil fatty ds are pepare y s ponifyi g benzene layer is washed several times with hot waterlinseed Oil h alc h lic alk li; in he present case 8 until the washsolution is neutral. Usually about 6 or 7 methanol solution of sodiumhydr xid Was p y washes are required. A purification step may beinterposed Upon neutralization and removal of the fatty acid compoatthis point. The purification involves agitating a mixture nent, amixture con aining 7% linolenic, 17% lin i of the washed benzene layerand 80 lbs. water containing 10 7% oleic, and 9% saturate fa y ids W sObtained- 8 lbs. sodium hydroxide or other alkaline refining agent 1,000g of this mlXeCl f t y acid c mposition Was for 1 hour while maintainingthe temperature at about added to a ution O 2, g ams o a in 5 150Benzene is. then removed by distillation at atmosl t s f methanol. Themetha s lu on f ur a w pheric pressure, the final traces being removedunder agitated vigorously during addition of the f tty ac dsvacuum.Physical constants of the starting linseed oil Apreeipitate formed andthe mixture was allowed to stand and the epoxidised product are asfollows: overnight at o p r r e prec pi ed urea F 1 complexes were thenfiltered off and disrwuded,- While eed Analysls tfigglfgg the filtratewas distilled under vacuum to remove the I V l 182 0 4 5 major portionof methanol. The fatty acid mixture derived f 1931) j fr m the filtratwa h n wa hed wi h wa er o rem e g.r .4--. 39 09 excess urea. Afterdrying, the product which consisted of i g A 425 grams of an oily liquidwas analyzed. It was found geroxideoNoluuLh 3 to have an iodine value of2 41 as compared to an iodine 51 5 555522 j 1 0:19 value of the mixtureof fatty acids prior to the urea treatment of 181.4.

Example H This urea fractionation technique was also employed Thepreparation of the lower alkyl esters is as follows: in the treatment fy fi l l ty i a d t Oil Linseed oil is reacted with the appropriatelower monofatty acids. The composition of the f t y acid m Xture hydricalcohol by refluxing the alcohol containing potasfollows:

Soybean Oil Distilled Tall Oil AnalyticalData Original After UreaOriginal After Urea i1 Treatment Oil Treatment Iodine Value of FattyAcid Mixture 123.0 190.7 124.2 109 4 Percent Linolenic Acid.- 6. 8. 19.0. Percent Linoleic Acid..- 40. 7 76. 4 47. 0 9.0. 2 Percent Oleic Acid39. 9 3. 5 45. 0 9. 0 Percent Saturated Acid 11. 9. 1. 1 Z. 0 0.8

sium hydroxide with the oil. The glycerol which is freed The yield ofhighly unsaturated soybean oil fatty acids in the ester interchange isdrawn off, and more alcoholic was while the yield of highly unsaturatedtall oil caustic is added to the reaction mixture and refluxing fattyacids was 51%. Other methods .of concentrating continued. After 3 passesof alcoholic alkali the free 45 unsaturated fatty acids are known in theart. glycerol content of the, product; is less than 0.3%. The Each ofthe fractionated fatty acid mixtures noted first pass with the primaryalcohol involves about 30% above was esterified with n-butanol' in thefollowing manby weight of the alcohol based upon the linseed oil whilener: A mixture of 500 grams of the fatty acids-and 250 the 2 subsequentpasses involve. the use of about grams, of n-butanol was heated, along.with; 10. gramsof by weight of the alcohol. Epoxidation of themonohydric 50 p-toluene sulfonic acid, in a. glass. vessel fitted. witha. realcohol esters of the linseed oil fatty acids is carried out fluxcondenser and a water trap for a time suflicient to rein the manner ofExample I. The methyl, ethyl, propyl, move the theoretical amount ofwater. A water trap ren-butyl, isobutyl, and n-octyl and benzyl estersof epoxiflux condenser equipped with a calibrated receiver is dizedlinseed oil fatty acids were. prepared. The physical suitable for thispurpose. After the theoretical amount of constants of these esters is asfollows: Water had been accumulated in the trap, the reaction Ester orPercent mixture was cooled, washed with a 5% aqueous solution LinseedInitial Final Percent Percent Oximna of sodium carbonate, and finallywashed with Water until ggg IV IV g i OXlmne gg g g the washings wereneutral to litmus. The excess alcohol Portion was steam distilled fromthe ester and after drying the 1... Methyl..- 185 7.2 0.04 3.9 0.3Product was analyzed 5:: flight: ii? iii 3:33 $13 3:35 Bummer SammieIodine A 4..- n-ButyL; 154.5 7.4 0.07 7.0 9.0 mm Value Value 5 isobutl..- 150.5 3.5 0.04 7 5 8.9

Lmseel O11 Fatty Acids 164. 9 200. 0 0. 93 gg g fi Soybean Oil FattyAcids 107.4 100.1 0. 30 Tall O11 FattyAclds 165.9 143.9 0.65

*The benzyl ester was prepared from the achid chloride of the linseedacid mixture and benzyl alcohol in pyridine. It After epoxldatlon ofthese butyl esters in accordance was epoxldized in the manner of ExampleI. with the procedure described in Example I, the final The upgrading orconcentration of more unsaturated epoxidized esters had the followingphysical characterfatty acids and the removal of the more saturatedfatty istics:

Butyl Ester of Saponifi- Acid No. Iodine PercentOxicatlon No. Value raneOxygen Linseed Oil Fatty Acids 148.7 1.10 7.6 0.39 Soybean Oil FattyAcids 151.0 0. 41 4.9 7.93 Tall Oil Fatty Acids 152.0 0. 03 3.2 7.47

It will be noted that, while the percent oxirane oxygen for the butylesters is less than 8.8, the percent oxirane oxygen in the fatty acid iswell above this lower limit. These compositions are most effective,particularly as regards handling characteristics and the provision ofsuperior low temperature flexibility characteristics in films preparedfrom vinyl halide resins containing these lower alkyl esters of mixedepoxidized fatty acid esters.

Flexible films which are prepared from the vinyl resinhigh oxiranecomposition exhibit substantial freedom from plasticizer migration andexudation and also possess highly desirable handling characteristics.These films are prepared by well-known milling, calendering, orextruding techniques. It is possible, because of the unexpectedly highcompatability of the expoxide and resin, to employ the high oxiranefatty ester as the sole plasticizer for the vinyl to obtain the desiredflexibility. Moreover, troublesome heat degradation of the vinyl halideis held to a minimum by the plasticizer. This improved resistance toheat-induced deterioration allows for the omission of stabilizercompositions, such as the metal salts mentioned previously. This abilityto dispense with metal salt stabilizers is most important in thepreparation of food films, since films designed for use in the packagingof foods should be free of extractable toxic metal salts and other toxicsubstances.

The efiect of varying amounts of the plasticizer on milled filmsprepared from the vinyl halide-high oxirane mixture is shown in ExampleIV which follows:

Example IV Parts Polyvinyl chloride (Geon 103 EP) 100 Epoxidized linseedoil X Zinc stearate 1 Each of the dry blends was milled at 320 F. forminutes and films of 2-4 mils thickness were taken for determination ofthe physical data for each. The following table shows the physical datafor films prepared from mixes containing varying amounts of the epoxide:

Parts Epoxi- Ultimate Corrected Modulus Weatheromdized Linseed TensileElongation at 100% eter Oil in above Strength, at Break, Elongation,Stability Formulation p.s.i. percent p.s.i. (hrs) An AtlasSunshine-Carbon Are type weatherorneter Model XW was employed.

Example V Extruded films were prepared from formulations containingvarying levels of the high oxirane linseed oil. The dry blend of theresin plasticizer compound was pelletized and the pellets we e R5 10 an.cxtruder which produced the film in the form of an inflated tube. Theformula for the dry blend is as follows:

The films prepared showed the following physicals:

Parts Expoxi Ultimate Corrected Molulns Tearing dized Linseed TensileElongation at Force, Oil in Above Strength, at Break, Elongation, g./milFormulation p.s.i. percent p.s.i.

Lrepresents the physicals measured in the longitudinal direction of thefilm. T-represeuts the physicals measured in the transverse direction ofthe film.

Example VI Milled films were prepared from the following compositionswhich were formulated as dry blends in the mixer:

Parts Polyvinyl chloride (Geon 103 EP) 100 Butyl ester epoxidizedlinseed oil fatty acids X Barium-cadmium laurate stabilizer 2 Chelatingcompound 1 Mixture was milled for 5 minutes at 340 F.

Parts Longitudinal Transverse Butyl Ester Epoxidized Ultimate CorrectedUltimate Corrected Linseed Oil Tensile Elongation Tensile ElongationFatty Oil Strength, at Break, Strength, at Break,

psi. percent p.s.i. percent It was noted that the sample containing 4parts butyl ester can be processed much more easily than the samecontaining no plasticizer. While elongation and tensile strength are notgreatly afiected by the plasticizer, the heat stability of the mix isimproved significantly.

Example VII The following ingredients were dryblended in a Hobart mixer:

1 One mol of tetraethylene pentamine mixed with 5 mols of stearic acidand heated to a temperature of 180 C. for about 2 hours.

The formulation is extruded to provide thin films of about 1-10 milsthickness. The film is clear, transparent, and glossy and has very goodflexibility as well as freedom from static. The polyvinyl chloridecomposition exhibits very desirable handling characteristics, and thereis a minimum of burning and charring in the extruder. This resistance toheat degradation results primarily from the superior stability of theformulation.

Obviously, many modifications and variations of the invention ashereinbefore set forth may be made without departing from the spirit andscope thereof, and therefore only such limitations should be imposed asare indicated in the appended claims.

We claim:

1. A polyvinyl resin composition comprising: a vinyl halide polymerwhich is free of polyunsaturated monomers and which contains at least50% polymerized vinyl halide units and glyceride esters ofoxirane-containing fatty acids of 1030 carbons having a low amount ofhydroxyl substitution and a low polymer content, the oxirane groupsbeing present in the fatty acyl portion of said esters, the oxiranecontent of said esters being in the range 8.8-9.2% and the iodine valueless than about 12.

2. A polyvinyl resin composition comprising a vinyl halide polymer whichis free of polyunsaturated monomers and which contains at least 50%vinyl halide units and lower alkyl alcohol esters of epoxidized linseedoil fatty acids having a low amount of hydroxyl substitution and a lowpolymer content, the oxirane content of said fatty acids being about88-92% and the iodine value less than about 1-2.

3. A polyvinyl resin composition comprising a homopolymer of polyvinylchloride and glyceryl esters of cpoxidized linseed oil fatty acids, theoxirane content of said fatty acids being about 8.89.2% and having a lowamount of hydroxyl substitution as measured by an infrared absorptivityat 2.9 microns of .02 maximum, a low polymer content as measured by aviscosity not substantially in excess of 8.8 poises and the iodine valueless than about 12.

4. A polyvinyl resin composition comprising a vinyl halide resincontaining at least 90% vinyl chloride units and a plasticizer, saidplasticizer having a low amount of hydroxy substitution and a lowpolymer content and being a mixture lower alkyl alcohol esters ofepoxidized fatty acids wherein said mixture comprises esters ofepoxidized linoleic acid and epoxidized linolenic acid, the epoxidizedlinoleic acid comprising less than about 35% based on said fatty acidmixture, and the combined epoxidized linoleic-linolenic acid content ofsaid mixture comprising more than about 60% based on said fatty acidmixture, the oxirane content of said epoxidized fatty acid mixture beingabout 88-92% and the iodine value less than about 12.

5. Epoxidized triglyceride esters of 1030 carbon fatty acids, saidtriglyceride having an oxirane oxygen content of about 8.89.2%, a lowamount of hydroxyl substitution as measured by an infrared absorptivityat 2.9 microns of .02 maximum, a low polymer content as measured by aviscosity not substantially in excess of 8.8 poises and an iodine valueless than 12.

6. Substantially completely epoxidized linseed oil having an iodinevalue of 12 maximum, an oxirane oxygen content of about 8.89.2%, aninfrared absorptivity at 2.9 microns of 0.02 maximum, and a viscosity of8.8 poises maximum.

References Cited UNITED STATES PATENTS 3,047,415 7/1962 Rhodes et a1.260-23X 3,196,117 7/1965 Boller 260-23 3,230,189 1/1966 Johnson et al260-23 X 2,556,145 6/ 1951 Niederhauser 260-18 2,964,484 12/1960 Findleyet al 260-23 X 2,993,920 7/1961 Budde et al. -2 260-18 3,008,911 11/1961Douglas 260-23 X 3,070,608 12/1962 Kuester et al 260-23 X 3,119,7111/1964 Starmann et a1 260-18 OTHER REFERENCES Becco Bulletin,Epoxidation and Hydroxylation with Hydrogen Peroxide and Peracetic Acid,pp. i, ii, 1-3, 34-36, 39, 46, 47 Becco Bulletin 69, October 1955.

Industrial Oil and Fat Products, Interscience Publishers Inc., New York,Second Edition, 1951 (Treatise by Alton E. Bailey).

DONALD E. CZAJA, Primary Examiner.

LEON I. BERCOVITZ, JAMES A. SEIDLECK,

Examiners. R. W. GRIFFIN, Assistant Examiner.

1. A POLYVINYL RESIN COMPOSITION COMPRISING: A VINYL HALIDE POLYMERWHICH IS FREE OF POLYUNSATURATED MONOMERS AND WHICH CONTAINS AT LEAST50% POLYMERIZED VINYL HALIDE UNITS AND GLYCERIDE ESTERS OFOXIRANE-CONTAINING FATTY ACIDS OF 10-30 CARBONS HAVING A LOW AMOUNT OFHYDROXYL SUBSTITUTION AND A LOW POLYMER CONTENT, THE OXIRANE GROUPSBEING PRESENT IN THE FATTY ACYL PORTION OF SAID ESTERS, THE OXIRANECONTENT OF SAID ESTERS BEING IN THE RANGE 8.8-9.2% AND THE IODINE VALUELESS THAN ABOUT 12.